Liquid detergent compositions comprising pH tuneable amido-gellants, and processes for making

ABSTRACT

The invention is directed to a fluid detergent composition comprising a pH tuneable amido gellant and a surfactant, and a method for structuring said composition.

FIELD OF THE INVENTION

The present invention relates to fluid detergent compositions comprisinga structurant that is compatible with a broad range of detergentcompositions and does not affect product clarity, and a process formaking them.

BACKGROUND OF THE INVENTION

Today's consumers desire high performance liquid detergent compositionshaving sufficient structuring to give a rich impression and stabilizeperformance ingredients. External structurants for providing rheologicalbenefits to fluid detergent compositions include those derived fromcastor oil, fatty acids, fatty esters, or fatty soap water-insolublewaxes. However, the required performance ingredients often complicatethe addition of external structurants known in the art and may even beincompatible with them. For instance, many external structurants aredegraded by performance ingredients, such as enzymes, including proteaseand lipase (lipase hydrolyses ester bonds present in castor oilderivatives), which are desirable for improved low temperature cleaning.They are also often incompatible with low pH and peroxide bleaches. Inaddition, external structurants generally require the use of structurantpremixes incorporating large amounts of water. Such structurant premixesare unsuitable for compact detergents and for unit-dose applications.

Amido-gellants provide a solution for structuring fluid detergentcompositions while also being compatible with a broad range of optionaldetergent ingredients, such as bleaches and/or enzymes. They alsoprovide an aesthetically pleasing pour profile without negativelyimpacting the composition clarity. They can be formulated intostructurant premixes that are entirely water-free. However, mostamido-gellants require premixes that have to be heated to as high as100° C. to reduce the viscosity to a level where they can be easilymixed with a detergent composition. Since ingredients such as enzymesand perfumes start to degrade at temperatures as low as 50° C., theymust be added after the amido-gellant, and after a cooling step.

As such, a need remains for a structurant for fluid detergentcompositions, that is compatible with a broad range of ingredients(including heat-sensitive ingredients such as enzymes), while also beingeasy to incorporate in to the composition without requiring excessiveheating.

SUMMARY OF THE INVENTION

The fluid detergent composition of the present invention comprises: from1% to 70% by weight of a surfactant selected from the group consistingof: anionic, nonionic surfactants and mixtures thereof; and from 0.01 wt% to 10 wt % of a pH tuneable amido-gellant as an external structuringsystem; wherein the pH tuneable amido-gellant has a pKa of from 1 to 30.Another aspect of the present invention provides for a process formaking such fluid detergent compositions comprising a pH tuneable amidogellant.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 details G′ and G″ within the linear viscoelastic region and theoscillation stress at the point where G′ and G″ cross over as a measurefor gel strength.

FIG. 2 details G′ and G″ cross over as a measure of restructuringkinetics.

DETAILED DESCRIPTION OF THE INVENTION

Fluid detergent compositions as described herein include but are notlimited to consumer products such as: shampoos; skin cleaners andexfolients; shaving liquids, foams and gels; products for treatingfabrics, hard surfaces and any other surfaces in the area of fabric andhome care, including: dishwashing, laundry cleaning, laundry and rinseadditives, hard surface cleaning including floor and toilet bowlcleaners; products relating to oral care including toothpastes and gelsand whiteners. A particularly preferred embodiment of the invention is a“fluid laundry detergent composition”. As used herein, “fluid laundrydetergent composition” refers to any laundry treatment compositioncomprising a fluid capable of wetting and cleaning fabric e.g.,clothing, in a domestic washing machine.

The fluid detergent composition can include solids or gases in suitablysubdivided form, but the overall composition excludes product formswhich are non-fluid overall, such as tablets or granules. The fluiddetergent compositions preferably have densities in the range from of0.9 to 1.3 grams per cubic centimeter, more preferably from 1.00 to 1.10grams per cubic centimeter, excluding any solid additives but includingany bubbles, if present.

The fluid detergent compositions of the invention may be opaque,semi-transparent or even clear. When clarity of the fluid detergentcomposition is desired, the fluid detergent composition has a turbidityof from 5 NTU to less than 3000 NTU, preferably less than 1000 NTU, morepreferably less than 500 NTU and most preferably less than 100 NTU.

All percentages, ratios and proportions used herein are by weightpercent of the composition, unless otherwise specified. All averagevalues are calculated “by weight” of the composition or componentsthereof, unless otherwise expressly indicated.

Anionic and Nonionic Surfactants:

Detergent compositions of the present invention comprise from 1% to 70%,preferably from 5% to 60% by weight, more preferably from 10% to 50%,and most preferably from 15% to 45% by weight of a surfactant selectedfrom the group consisting of: anionic, nonionic surfactants and mixturesthereof. The preferred ratio of anionic to nonionic surfactant is from100:0 (i.e. no nonionic surfactant) to 5:95, more preferably from 99:1to 1:4, most preferably 5:1 to 1.5:1.

1. Anionic Surfactants:

The fluid detergent compositions of the present invention preferablycomprises from 1 to 50%, preferably from 5 to 40%, more preferably from10 to 30% by weight of one or more anionic surfactants. Preferredanionic surfactant are selected from the group consisting of: C11-C18alkyl benzene sulfonates, C10-C20 branched-chain and random alkylsulfates, C10-C18 alkyl ethoxy sulfates, mid-chain branched alkylsulfates, mid-chain branched alkyl alkoxy sulfates, C10-C18 alkyl alkoxycarboxylates comprising 1-5 ethoxy units, modified alkylbenzenesulfonate, C12-C20 methyl ester sulfonate, C10-C18 alpha-olefinsulfonate, C6-C20 sulfosuccinates, and mixtures thereof. However, bynature, every anionic surfactant known in the art of detergentcompositions may be used, such as those disclosed in “Surfactant ScienceSeries”, Vol. 7, edited by W. M. Linfield, Marcel Dekker. However, thecompositions of the present invention comprise preferably at least onesulphonic acid surfactant, such as a linear alkyl benzene sulphonicacid, or the water-soluble salt forms.

Anionic sulfonate or sulfonic acid surfactants suitable for use hereininclude the acid and salt forms of linear or branched C5-C20, morepreferably C10-C16, most preferably C11-C13 alkylbenzene sulfonates,C5-C20 alkyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C5-C20 sulfonated polycarboxylic acids, and mixturesthereof. The aforementioned surfactants can vary widely in their2-phenyl isomer content.

Anionic sulphate salts suitable for use in compositions of the inventioninclude: primary and secondary alkyl sulphates, having a linear orbranched alkyl or alkenyl moiety having from 9 to 22 carbon atoms, morepreferably from 12 to 18 carbon atoms; beta-branched alkyl sulphatesurfactants; and mixtures thereof.

Mid-chain branched alkyl sulphates or sulfonates are also suitableanionic surfactants for use in the compositions of the invention.Preferred are the C5-C22, preferably C10-C20 mid-chain branched alkylprimary sulphates. When mixtures are used, a suitable average totalnumber of carbon atoms for the alkyl moieties is preferably within therange of from 14.5 to 17.5. Preferred mono-methyl-branched primary alkylsulphates are selected from the group consisting of the 3-methyl to13-methyl pentadecanol sulphates, the corresponding hexadecanolsulphates, and mixtures thereof. Dimethyl derivatives or otherbiodegradable alkyl sulphates having light branching can similarly beused.

Other suitable anionic surfactants for use herein include fatty methylester sulphonates and/or alkyl ethyoxy sulphates (AES) and/or alkylpolyalkoxylated carboxylates (AEC). Mixtures of anionic surfactants canbe used, for example mixtures of alkylbenzenesulphonates and AES.

The anionic surfactants are typically present in the form of their saltswith alkanolamines or alkali metals such as sodium and potassium.Preferably, the anionic surfactants are neutralized with alkanolaminessuch as monoethanolamine or triethanolamine, and are fully soluble inthe liquid phase.

2. Nonionic Surfactants:

The fluid detergent compositions of the present invention preferablycomprise up to 30%, preferably from 1 to 15%, more preferably from 2 to10% by weight of one or more nonionic surfactants. Suitable nonionicsurfactants include, but are not limited to C12-C18 alkyl ethoxylates(“AE”) including the so-called narrow peaked alkyl ethoxylates, C6-C12alkyl phenol alkoxylates (especially ethoxylates and mixedethoxy/propoxy), block alkylene oxide condensate of C6-C12 alkylphenols, alkylene oxide condensates of C8-C22 alkanols and ethyleneoxide/propylene oxide block polymers (Pluronic®-BASF Corp.), as well assemi polar nonionics (e g , amine oxides and phosphine oxides). Anextensive disclosure of suitable nonionic surfactants can be found inU.S. Pat. No. 3,929,678.

Alkylpolysaccharides such as disclosed in U.S. Pat. No. 4,565,647 arealso useful nonionic surfactants for compositions of the invention. Alsosuitable are alkyl polyglucoside surfactants. In some embodiments,suitable nonionic surfactants include those of the formulaR₁(OC₂H₄)_(n)OH, wherein R₁ is a C10-C16 alkyl group or a C8-C12 alkylphenyl group, and n is from 3 to about 80. In some embodiments, thenonionic surfactants may be condensation products of C12-C15 alcoholswith from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g.,C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide permole of alcohol. Additional suitable nonionic surfactants includepolyhydroxy fatty acid amides of the formula:

wherein R is a C9-C17 alkyl or alkenyl, R₁ is a methyl group and Z isglycidyl derived from a reduced sugar or alkoxylated derivative thereof.Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methylN-1-deoxyglucityl oleamide.

External Structurant:

The external structurant preferably imparts a shear thinning viscosityprofile to the fluid detergent composition, independently from, orextrinsic from, any structuring effect of the detersive surfactants ofthe composition. Preferred external structurants include those whichprovide a pouring viscosity from 50 cps to 20,000 cps, more preferablyfrom 200 cps to 10,000 cps, most preferably from 500 cps to 7,000 cps.The fluid detergent composition preferably has a resting viscosity of atleast 1,500 cps, preferably at least 10,000 cps, more preferably atleast 50,000 cps. This resting (low stress) viscosity represents theviscosity of the fluid detergent composition under gentle shaking in thepackage and during transportation. Alternatively, the fluid detergentcomposition may be a thixotropic gel. Such compositions may have aresting viscosity of from 10,000 cps to 500,000 cps, preferably from100,000 cps to 400,000 cps, more preferably from 200,000 to 300,000. Thepreferred shear-thinning characteristics of the fluid detergent isdefined as a ratio of low stress viscosity to pouring viscosity of atleast 2, preferably at least 10, more preferably at least 100, up to2000.

The pouring viscosity is measured at a shear rate of 20 sec⁻¹, which isa shear rate that the fluid detergent composition is typically exposedto during pouring. The resting (low stress) viscosity is determinedunder a constant stress of 0.1 Pa during a viscosity creep experimentover a 5 minute interval. Rheology measurements over the 5 minuteinterval are made after the composition has rested at zero shear ratefor at least 10 minutes, between loading the sample in the rheometer andrunning the test. The data over the last 3 minutes are used to fit astraight line, and from the slope of this line, the low stress viscosityis calculated. The viscosity is measured at 21° C. using a TA AR 2000(or AR G2) rheometer with a 40 mm stainless steel plate having a gap of500 microns.

1. pH Tuneable Amido Gellant

The pH tuneable amido gellant provides the fluid detergent compositionwith a viscosity profile that is dependent on the pH of the composition.The pH tuneable amido gellants comprise at least one pH sensitive group.When a pH tuneable amido gellant is added to a polar protic solvent suchas water, it is believed that the nonionic species form the viscositybuilding network while the ionic species are soluble and do not form aviscosity building network. By increasing or decreasing the pH(depending on the selection of the pH-sensitive groups) the amidogellant is either protonated or deprotonated. Thus, by changing the pHof the solution, the solubility, and hence the viscosity buildingbehaviour, of the amido gellant can be controlled. By careful selectionof the pH-sensitive groups, the pKa of the amido gellant can betailored. Hence, the choice of the pH-sensitive groups can be used toselect the pH at which the amido gellant builds viscosity.

The fluid detergent composition comprises from 0.01 wt % to 10 wt %,preferably from 0.05 wt % to 5 wt %, more preferably from 0.1 wt % to 2wt %, most preferably from 0.4 wt % to 1 wt %, of a pH tuneableamido-gellant as an external structuring system. In an alternativeembodiment, the fluid detergent composition comprises from 0.1 wt % to0.5 wt % of the pH tuneable amido-gallant. The pH tuneable amido-gellanthas a formula selected from the group consisting of:

wherein R₁ and R₂ are aminofunctional end-groups; L₁ is a backbonemoiety having molecular weight from 14 to 500 g/mol; and at least one ofL₁, R₁ or R₂ comprises a pH-sensitive group.

wherein R₅ is an aminofunctional moiety; L₂ is a backbone moiety havingmolecular weight from 14 to 500 g/mol; and at least one of L₂ or R₅comprises a pH-sensitive group;

-   -   and mixtures thereof;    -   wherein the pH tuneable amido-gellant has a pKa of from 1 to 30,        preferably a pKa of from 1.5 to 14.

The pH tuneable amido gellant comprises at least one amido functionalgroup, and further comprises at least one pH-sensitive group.Preferably, the pH tuneable amido gellant has a molecular weight from150 to 1500 g/mol, more preferably from 300 g/mol to 900 g/mol, mostpreferably from 400 g/mol to 700 g/mol.

In one embodiment, the pH tuneable amido gellant has the followingstructure [I]:

wherein R₁ and R₂ are aminofunctional end-groups; L₁ is a backbonemoiety having molecular weight from 14 to 500 g/mol; and at least one ofL₁, R₁ or R₂ comprises a pH-sensitive group.

L₁ preferably has the formula:L ₁ =A _(a) −B _(b) −C _(c) −D _(d),   [III]wherein: (a+b+c+d) is from 1 to 20; and A, B, C and D are independentlyselected from the linking groups consisting of:

Preferably, A, B, C and D are independently selected from the linkinggroups consisting of:

*the arrow indicates up to 4 substitutions in the positions indicated,and X⁻ an anion Preferably, L₁ is selected from C2 to C20 hydrocarbylchains, more preferably C6 to C12, most preferably C8 to C10.

In a preferred embodiment: R₁ is R₃ or

R₂ is R₄ or

wherein each

AA is independently selected from the group consisting of:

R″, H,

and R₃ and R₄ independently have the formula:(L′)_(o)-(L″)_(q)-R,   [IV]wherein: (o+q) is from 1 to 10; L′ and L″ are linking groups,independently selected from the same groups as A, B, C and D in equation[III]; and R, R′ and R″ are independently selected either from thepH-sensitive-groups consisting of:

*the arrow indicates up to 4 substitutions in the positions indicated, nand m are integers from 1 to 20

or from the non-pH-sensitive groups consisting of:

such that at least one of R, R′ and R″ comprises a pH-sensitive group.Preferably, R comprises the pH-sensitive group.

In other embodiments, at least some of R, R′ and R″ are independentlyselected from the group of pH-sensitive molecules consisting of:

In a preferred embodiment, the pH tuneable amido gellant havingstructure [I] is characterized in that: L₁ is an aliphatic linking groupwith a backbone chain of from 2 to 20 carbon atoms, preferably—(CH₂)_(n)— wherein n is selected from 2 to 20, and both R₁ and R₂ havethe structure:

AA is preferably selected from the group consisting of:

or from the group consisting of:

and R is preferably selected from the pH-sensitive groups consisting of:

or from the group:

In another embodiment, two or more of L₁, L′ and L″ are the same group.

The pH tuneable amido gellant molecule described in formula [I] can besymmetric with respect to the L₁ entity or can be asymmetric. Withoutintending to be bound by theory, it is believed that symmetric pHtuneable amido gellant molecules allow for more orderly structurednetworks to form, whereas compositions comprising one or more asymmetricpH tuneable amido gellant molecules can create disordered networks.

Suitable pH tuneable amido gellants having structure [I] may be selectedfrom table 1 and table 2, and mixtures thereof. More preferably, the pHtuneable amido gellants, having structure [I], are selected from table2, and mixtures thereof.

In another embodiment, the pH tuneable amido gellant has the structure[II]:

wherein R₅ is an aminofunctional moiety; L₂ is a backbone moiety havingmolecular weight from 14 to 500 g/mol; and at least one of L₂ or R₅comprises a pH-sensitive group;

L₂ preferably has the formula:L ₂ =A _(a) −B _(b) −C _(c) −D _(d)-R″″,   [V]wherein: (a+b+c+d) is from 1 to 20; and R′″ is either a pH-sensitivegroup or a non-pH-sensitive groups (selected from the same groups as R,R′ and R″ for structure [I]).

Preferably, L₂ is selected from C2 to C20 hydrocarbyl chains, morepreferably C6 to C12, most preferably C8 to C10.

R₅ preferably has the formula:

wherein: AA is independently selected from the same group of AA as forstructure [I]; (e+f+g) is from 0 to 20, more preferably from 1 to 3.

At least one of AA, R or R′″ comprises a pH sensitive group. Preferably,R comprises the pH sensitive group.

In a preferred embodiment, the pH tuneable amido gellant havingstructure [II] is characterized in that: L₂ is an aliphatic linkinggroup with a backbone chain of from 2 to 20 carbon atoms, preferably—(CH₂)_(n)—CH₃ wherein n is selected from 2 to 20, and R₅ has thestructure:

wherein: each AA is independently selected from the group consisting of:

or from the group consisting of:

and R is selected from the pH-sensitive groups consisting of:

or from the group:

Suitable pH tuneable amido gellants having structure [II] include thestructures selected from table 3, and mixtures thereof.

pH Tuneable Amido Gellant Examples of Use in the Present Invention:

TABLE 1 Non-limiting examples of pH tuneable amido gellants havingstructure [I] of use in fluid detergent compositions of the invention:

N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis-N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis-(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis-N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis-(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis-N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis-(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis-(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide

(6S,13S)-6,13-diisopropyl-4,7,12,15-tetraoxo-5,8,11,14-tetraazaoctadecane-1,18-dioic acid(6S,14S′)-6,14-diisopropyl-4,7,13,16-tetraoxo-5,8,12,15-(6S,15S)-6,15-diisopropyl-4,7,14,17-tetraoxo-5,8,13,16-tetraazanonadecane-1,19-dioic acid tetraazaeicosane-1,20-dioic acid(6S,16S)-6,16-diisopropyl-4,7,15,18-tetraoxo-5,8,14,17-(6S,17S)-6,17-diisopropyl-4,7,16,19-tetraoxo-5,8,15,18-tetraazaheneicosane-1,21-dioic acid tetraazadocosane-1,22-dioic acid(6S,18S)-6,18-diisopropyl-4,7,17,20-tetraoxo-5,8,16,19-(6S,19S)-6,10-diisopropyl-4,7,18,21-tetraoxo-5,8,17,20-tetraazatricosane-1,23-dioic acid tetraazatetracosane-1,24-dioic acid(6S,20S)-6,20-diisopropyl-4,7,19,22-tetraoxo-5,8,18,21-(6S,21S)-6,21-diisopropyl-4,7,20,23-tetraoxo-5,8,19,22-tetraazapentacosane-1,25-dioic acid tetraazahexacosane-1,26-dioic acid(6S,22S)-6,22-diisopropyl-4,7,21,24-tetraoxo-5,8,20,23-(6S,23S)-6,23-diisopropyl-4,7,22,25-tetraoxo-5,8,21,24-tetraazaheptacosane-1,27-dioic acid tetraazaoctacosane-1,28-dioic acid

N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis(3-methyl-N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(3-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)N,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(3-methyl-N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(3-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(3-methyl-N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(3-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(3-methyl-N,N′-(2S,2′S)-1,1′-(nonane-1,9-diylbis(azanediyl))bis(3-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl )benzamide)methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(3-methyl-N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(3-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide)

TABLE 2 Non-limiting examples of pH tuneable amido gellants havingstructure [I] of use in fluid detergent compositions of the invention:

N,N′-(2S,2′S)-1,1′-(nonane-1,9- N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(3-methyl-1-oxobutane-diylbis(azanediyl))bis(3-methyl-1-oxobutane- 2,1-diyl)diisonicotinamide2,1-diyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(undecane-1,11-N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-diylbis(azanodiyl))bis(3-methyl-1-oxobutane- 2,1-diyl)diisonicotinamide2,1-diyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(tridecane-1,13-N,N′-(2S,2′S)-1,1′-(tetradecane-1,14-diylbis(azanediyl))bis(3-methyl-1-oxobutane-diylbis(azanediyl))bis(3-methyl-1-oxobutane- 2,1-diyl)diisonicotinamide2,1-diyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(hexadecane-1,16-N,N′-(2S,2′S)-1,1′-(octadecane-1,18-diylbis(azanediyl))bis(3-methyl-1-oxobutane-diylbis(azanediyl))bis(3-methyl-1-oxobutane- 2,1-diyl)diisonicotinamide2,1-diyl)diisonicotinamide

N,N′-(2S,2′S)-1,1′-(ethane-1,2- N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(butane-1,4-N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(hexane-1,6-N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(octane-1,8-N,N′-(2S,2′S)-1,1′-(nonane-1,9- diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(decane-1,10-N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(dodecane-1,12-N,N′-(2S,2′S)-1,1′-(tridecane-1,13-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(tetradecane-1,14-N,N′-(2S,2′S)-1,1′-(hexadecane-1,16-diylbis(azanediyl))bis(1-oxopropane-2,1-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamidediyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(octadecane-1,18-diylbis(azanediyl))bis(1-oxopropane-2,1- diyl)diisonicotinamide

N,N′-(2S,2′S)-1,1′-(ethane-1,2- diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(propane-1,3- N,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(1-oxo-3- diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(pentane-1,5- N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(1-oxo-3- diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(heptane-1,7- N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(1-oxo-3- diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamide N,N′-(2S,2′S)-1,1′-(nonane-1,9-N,N′-(2S,2′S)-1,1′-(decane-1,10- diylbis(azanediyl))bis(1-oxo-3-diylbis(azanediyl))bis(1-oxo-3- phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(undecane-1,11- N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3- diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(tridecane-1,13-N,N′-(2S,2′S)-1,1′-(tetradecane-1,14- diylbis(azanediyl))bis(1-oxo-3-diylbis(azanediyl))bis(1-oxo-3- phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(hexadecane-1,16-N,N′-(2S,2′S)-1,1′-(octadecane-1,18- diylbis(azanediyl))bis(1-oxo-3-diylbis(azanediyl))bis(1-oxo-3- phenylpropane-2,1-diyl)diisonicotinamidephenylpropane-2,1-diyl)diisonicotinamide

TABLE 3 Non-limiting examples of pH tuneable amido gellants havingstructure [II] of use in fluid detergent compositions of the invention:(2S)-2-[[2-(dodecanoylamino)acetyl]amino]propanoic acid

(2S)-2-[[2-[[2-(dodecanoylamino)acetyl]amino]acetyl]amino]propanoic acid

(2S)-2-[[2-(dodecanoylamino)acetyl]amino]-2-phenyl-acetic acid

(2S)-2-[[2-(dodecanoylamino)acetyl]amino]-3-methyl-butanoic acid

(2S)-2-[[2-(dodecanoylamino)acetyl]amino]acetic acid

(2S)-2-[[2-(hexadecanoylamino)acetyl]amino]propanoic acid

In certain embodiments of both types of pH tuneable amido gellantstructures, AA comprises at least one of: Alanine, β-Alanine andsubstituted Alanines; Linear Amino-Alkyl Carboxylic Acid; CyclicAmino-Alkyl Carboxylic Acid; Aminobenzoic Acid Derivatives; AminobutyricAcid Derivatives; Arginine and Homologues; Asparagine; Aspartic Acid;p-Benzoyl-Phenylalanine; Biphenylalanine; Citrulline;Cyclopropylalanine; Cyclopentylalanine; Cyclohexylalanine; Cysteine,Cystine and Derivatives; Diaminobutyric Acid Derivatives;Diaminopropionic Acid; Glutamic Acid Derivatives; Glutamine; Glycine;Substituted Glycines; Histidine; Homoserine; Indole Derivatives;Isoleucine; Leucine and Derivatives; Lysine; Methionine;Naphthylalanine; Norleucine; Norvaline; Ornithine; Phenylalanine;Ring-Substituted Phenylalanines; Phenylglycine; Pipecolic Acid,Nipecotic Acid and Isonipecotic Acid; Proline; Hydroxyproline;Thiazolidine; Pyridylalanine; Serine; Statine and Analogues; Threonine;Tetrahydronorharman-3-carboxylic Acid; 1,2,3,4-Tetrahydroisoquinolin;Tryptophane; Tyrosine; Valine; and combinations thereof.

The pH tuneable amido gellant molecule may also comprise protectivegroups, preferably from 1 to 2 protective groups, preferably twoprotective groups. Examples of suitable protective groups are providedin “Protecting Groups”, P. J. Kocienski, ISBN 313 135601 4, Georg ThiemeVerlag, Stutgart; and “Protective Groups in Organic Chemistry”, T. W.Greene, P. G. M. Wuts, ISBN 0-471-62301-6, John Wiley& Sons, Inc, NewYork.

The pH tuneable amido gellant preferably has a minimum gellingconcentration (MGC) of from 0.1 to 100 mg/mL in the fluid detergentcomposition, at the target pH of the composition, preferably from 0.1 to25 mg/mL, more preferred from 0.5 to 10 mg/mL in accordance with the MGCTest Method. The MGC as used herein can be represented as mg/ml or as awt %, where wt % is calculated as the MGC in mg/ml divided by 10. In oneembodiment, when measured in the fluid detergent composition, the MGC isfrom 0.1 to 100 mg/mL, preferably from 0.1 to 25 mg/mL of said pHtuneable amido gellant, more preferably from 0.5 to 10 mg/mL, or atleast 0.1 mg/mL, at least 0.3 mg/mL, at least 0.5 mg/mL, at least 1.0mg/mL, at least 2.0 mg/mL, at least 5.0 mg/mL of pH tuneable amidogellant. While the invention includes fluid detergent compositionshaving a pH tuneable amido gellant concentration either above or belowthe MGC, the pH tuneable amido gellants of the invention result inparticularly useful rheologies below the MGC.

2. Secondary External Structurants

In one embodiment, the pH tuneable amido gellant is combined with from0.01 to 5% by weight of one or more additional external structurants.Without being limited by theory, it is believed that the use of anadditional external structurant permits improved control of thetime-dependent gelling. For example, while the pH tuneable amido gellantprovides ultimately superior gelling, other external structurants mayprovide a temporary gel structure while the pH tuneable amido gellant isstill undergoing gelling. Non-limiting examples of suitable secondarystructurants are:

-   -   (i) Di-benzylidene Polyol Acetal Derivative: The fluid detergent        composition may comprise from 0.01% to 1% by weight of a        dibenzylidene polyol acetal derivative (DBPA), preferably from        0.05% to 0.8%, more preferably from 0.1% to 0.6%, most        preferably from 0.3% to 0.5%. In one embodiment, the DBPA        derivative may comprise a dibenzylidene sorbitol acetal        derivative (DBS).    -   (ii) Bacterial Cellulose: The fluid detergent composition may        also comprise from 0.005% to 1.0% by weight of a bacterial        cellulose network. The term “bacterial cellulose” encompasses        any type of cellulose produced via fermentation of a bacteria of        the genus Acetobacter such as CELLULON® by CPKelco U.S. and        includes materials referred to popularly as microfibrillated        cellulose, reticulated bacterial cellulose, and the like.    -   (iii) Coated Bacterial Cellulose: In one embodiment, the        bacterial cellulose is at least partially coated with a        polymeric thickener, for instance as prepared in accordance with        the methods disclosed in US 2007/0027108 paragraphs 8 to 19. In        one embodiment the at least partially coated bacterial cellulose        comprises from 0.1% to 5%, preferably from 0.5% to 3.0%, by        weight of bacterial cellulose; and from 10% to 90% by weight of        the polymeric thickener. Suitable bacterial cellulose include        the bacterial cellulose described above and suitable polymeric        thickeners include: carboxymethylcellulose, cationic        hydroxymethylcellulose, and mixtures thereof.    -   (iv) Non-Polymeric Crystalline Hydroxyl-Functional Materials: In        a preferred embodiment, the composition further comprises from        0.01 to 1% by weight of the composition of a non-polymeric        crystalline, hydroxyl functional structurant. Such non-polymeric        crystalline, hydroxyl functional structurants generally comprise        a crystallizable glyceride which can be pre-emulsified to aid        dispersion into the final fluid detergent composition. Preferred        crystallizable glycerides include hydrogenated castor oil or        “HCO” or derivatives thereof, provided that it is capable of        crystallizing in the liquid detergent composition.    -   (v) Polymeric Structuring Agents: Fluid detergent compositions        of the present invention may comprise from 0.01 to 5% by weight        of a naturally derived and/or synthetic polymeric structurant.        Examples of naturally derived polymeric structurants of use in        the present invention include: hydroxyethyl cellulose,        hydrophobically modified hydroxyethyl cellulose, carboxymethyl        cellulose, polysaccharide derivatives and mixtures thereof.        Examples of synthetic polymeric structurants of use in the        present invention include: polycarboxylates, polyacrylates,        hydrophobically modified ethoxylated urethanes, hydrophobically        modified non-ionic polyols and mixtures thereof. In another        preferred embodiment, the polyacrylate is a copolymer of        unsaturated mono- or di-carbonic acid and C1-C30 alkyl ester of        the (meth)acrylic acid.        Water and/or Non-Aminofunctional Organic Solvent:

The fluid detergent composition may be dilute or concentrated aqueousliquids. Alternatively, the fluid detergent composition may be almostentirely non-aqueous, and comprising a non-aminofunctional organicsolvent. Such fluid detergent compositions may comprise very littlewater, for instance, that may be introduced with other raw materials.Preferably, the fluid detergent composition comprises from 1% to 95% byweight of water and/or non-aminofunctional organic solvent. Forconcentrated detergents, the composition comprises preferably from 5% to70%, more preferably from 10% to 50%, most preferably from 15% to 45% byweight, water and/or non-aminofunctional organic solvent.

As used herein, “non-aminofunctional organic solvent” refers to anyorganic solvent which contains no amino functional groups. Preferrednon-aminofunctional organic solvents include monohydric alcohols,dihydric alcohols, polyhydric alcohols, glycerol, glycols, polyalkyleneglycols such as polyethylene glycol, and mixtures thereof. Highlypreferred are mixtures of solvents, especially mixtures of two or moreof the following: lower aliphatic alcohols such as ethanol, propanol,butanol, isopropanol; diols such as 1,2-propanediol or 1,3-propanediol;and glycerol. Also preferred are propanediol and mixtures thereof withdiethylene glycol where the mixture contains no methanol or ethanol.Thus embodiments of fluid detergent compositions of the presentinvention may include embodiments in which propanediols are used butmethanol and ethanol are not used.

Preferable non-aminofunctional organic solvents are liquid at ambienttemperature and pressure (i.e. 21° C. and 1 atmosphere), and comprisecarbon, hydrogen and oxygen.

Adjuncts Ingredients:

The fluid detergent composition of the present invention may alsoinclude conventional detergent ingredients selected from the groupconsisting of: cationic surfactants, amphoteric and/or zwitterionicsurfactants, non-aminofunctional organic solvents, enzymes, enzymestabilizers, amphiphilic alkoxylated grease cleaning polymers, clay soilcleaning polymers, soil release polymers, soil suspending polymers,bleaching systems, optical brighteners, hueing dyes, particulatematerial, perfume and other odour control agents, hydrotropes, sudssuppressors, fabric care benefit agents, pH adjusting agents, dyetransfer inhibiting agents, preservatives, non-fabric substantive dyesand mixtures thereof. Some of the optional ingredients which can be usedare described in greater detail as follows:

1. Additional Surfactants

The fluid detergent compositions of the present invention may compriseadditional surfactant selected from the group consisting: anionic,cationic, nonionic, amphoteric and/or zwitterionic surfactants andmixtures thereof.

Cationic surfactants: Suitable cationic surfactants can bewater-soluble, water-dispersable or water-insoluble. Such cationicsurfactants have at least one quaternized nitrogen and at least onelong-chain hydrocarbyl group. Compounds comprising two, three or evenfour long-chain hydrocarbyl groups are also included. Examples includealkyltrimethylammonium salts, such as C12 alkyltrimethylammoniumchloride, or their hydroxyalkyl substituted analogs. Compositions knownin the art may comprise, for example, 1% or more of cationicsurfactants.

Amphoteric and/or zwitterionic surfactants: Suitable amphoteric orzwitterionic detersive surfactants of use in the fluid detergentcompositions of the present invention include those which are known foruse in hair care or other personal care cleansing. Non-limiting examplesof suitable zwitterionic or amphoteric surfactants are described in U.S.Pat. No. 5,104,646 (Bolich Jr. et al.), U.S. Pat. No. 5,106,609 (BolichJr. et al.).

Amphoteric detersive surfactants suitable for use in the compositioninclude those surfactants broadly described as derivatives of aliphaticsecondary and tertiary amines in which the aliphatic radical can bestraight or branched chain and wherein one of the aliphatic substituentscontains from 8 to 18 carbon atoms and one contains an anionic groupsuch as carboxy, sulfonate, sulfate, phosphate, or phosphonate. Suitableamphoteric detersive surfactants for use in the present inventioninclude, but are not limited to: cocoamphoacetate, cocoamphodiacetate,lauroamphoacetate, lauroamphodiacetate, and mixtures thereof.

Zwitterionic detersive surfactants suitable for use in the compositionsare well known in the art, and include those surfactants broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from 8 to 18 carbon atoms and one contains an anionic groupsuch as carboxy, sulfonate, sulfate, phosphate or phosphonate.Zwitterionics such as betaines are suitable for this invention.

Furthermore, amine oxide surfactants having the formula:R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O (I) are also useful incompositions of the present invention. R is a relatively long-chainhydrocarbyl moiety which can be saturated or unsaturated, linear orbranched, and can contain from 8 to 20, preferably from 10 to 16 carbonatoms, and is more preferably C12-C16 primary alkyl. R′ is a short-chainmoiety preferably selected from hydrogen, methyl and —CH₂OH. When x+y+zis different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO isbutyleneoxy. Amine oxide surfactants are illustrated by C12-C14alkyldimethyl amine oxide.

Non-limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the compositions aredescribed in McCutcheon's, Emulsifiers and Detergents, 1989 Annual,published by M. C. Publishing Co., and U.S. Pat. Nos. 3,929,678,2,658,072; 2,438,091; 2,528,378.

2. Enzymes

The fluid detergent compositions of the present invention may comprisefrom 0.0001% to 8% by weight of a detersive enzyme which providescleaning performance and/or fabric care benefits. Such compositions havea neat pH of from 6 to 10.5. Suitable enzymes include proteases,amylases, cellulases, lipases, xylogucanases, pectate lyases,mannanases, bleaching enzymes, cutinases, and mixtures thereof. Apreferred enzyme combination comprises a cocktail of conventionaldetersive enzymes such as lipase, protease, cellulase and amylase.Detersive enzymes are described in greater detail in U.S. Pat. No.6,579,839.

For the enzymes, accession numbers or IDs shown in parentheses refer tothe entry numbers in the databases Genbank, EMBL and Swiss-Prot. For anymutations standard 1-letter amino acid codes are used with a *representing a deletion. Accession numbers prefixed with DSM refer tomicroorgansims deposited at Deutsche Sammlung von Mikroorganismen andZellkulturen GmbH, Mascheroder Weg 1b, 38124 Brunswick (DSMZ).

Protease: The composition may comprise a protease. Suitable proteasesinclude metalloproteases and/or serine proteases, including neutral oralkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).Suitable proteases include those of animal, vegetable or microbialorigin. In one aspect, such suitable protease may be of microbialorigin. The suitable proteases include chemically or geneticallymodified mutants of the aforementioned suitable proteases. In oneaspect, the suitable protease may be a serine protease, such as analkaline microbial protease or/and a trypsin-type protease. Examples ofsuitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO),Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM),Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391).

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.of porcine or bovine origin), including the Fusarium protease and thechymotrypsin proteases derived from Cellumonas (A2RQE2).

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens (P06832, NPRE_BACAM).

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus such as subtilisin 309 (P29600) and/or DSM 5483(P29599).

Suitable commercially available protease enzymes include: those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark);those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International; those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes; thoseavailable from Henkel/Kemira, namely BLAP (P29599 having the followingmutations S99D+S101 R+S103A+V104I+G159S), and variants thereof includingBLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP withS3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin withmutations A230V+S256G+S259N) from Kao.

Since certain pH tuneable amido-gellants may be hydrolyzed by proteaseenzymes, it is preferred that the protease enzyme is inhibited, such asthrough the use of a suitable enzyme stabilizer, unless the proteaseenzyme is encapsulated.

Amylase: Suitable amylases are alpha-amylases, including those ofbacterial or fungal origin. Chemically or genetically modified mutants(variants) are included. A preferred alkaline alpha-amylase is derivedfrom a strain of Bacillus, such as Bacillus licheniformis, Bacillusamyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, orother Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB12513, sp 707, DSM 9375, DSM 12368, DSMZ no. 12649, KSM AP1378, KSM K36or KSM K38. Preferred amylases include:

(a) alpha-amylase derived from Bacillus licheniformis (P06278,AMY_BACLI), and variants thereof, especially the variants withsubstitutions in one or more of the following positions: 15, 23, 105,106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243,264, 304, 305, 391, 408, and 444.

(b) AA560 amylase (CBU30457, HD066534) and variants thereof, especiallythe variants with one or more substitutions in the following positions:26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with the wild-type enzymefrom Bacillus SP722 (CBU30453, HD066526), especially variants withdeletions in the 183 and 184 positions.

Suitable commercially available alpha-amylases are Duramyl®, Liquezyme®Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, StainzymePlus®, Fungamyl® and BAN® (Novozymes A/S), Bioamylase® and variantsthereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. m.b.H,Austria), Rapidase®, Purastar®, Optisize HT Plus®, Enzysize®, Powerase®and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM®(KAO, Japan). Preferred amylases are Natalase®, Stainzyme® and StainzymePlus®.

Cellulase: The composition may comprise a cellulase. Suitable cellulasesinclude those of bacterial or fungal origin. Chemically modified orprotein engineered mutants are included. Suitable cellulases includecellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium,Thielavia, Acremonium, e.g., the fungal cellulases produced fromHumicola insolens, Myceliophthora thermophila and Fusarium oxysporum.

Commercially available cellulases include Celluzyme®, and Carezyme®(Novozymes A/S), Clazinase®, and Puradax HA® (Genencor InternationalInc.), and KAC-500(B)® (Kao Corporation).

In one aspect, the cellulase can include microbial-derivedendoglucanases exhibiting endo-beta-1,4-glucanase activity (E.C.3.2.1.4), including a bacterial polypeptide endogenous to a member ofthe genus Bacillus which has a sequence of at least 90%, 94%, 97% andeven 99% identity to the amino acid sequence SEQ ID NO:2 in U.S. Pat.No. 7,141,403) and mixtures thereof. Suitable endoglucanases are soldunder the tradenames Celluclean® and Whitezyme® (Novozymes A/S,Bagsvaerd, Denmark).

Preferably, the composition comprises a cleaning cellulase belonging toGlycosyl Hydrolase family 45 having a molecular weight of from 17 kDa to30 kDa, for example the endoglucanases sold under the tradenameBiotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).

Highly preferred cellulases also exhibit xyloglucanase activity, such asWhitezyme®.

Lipase: The composition may comprise a lipase. Suitable lipases includethose of bacterial or fungal origin. Chemically modified or proteinengineered mutants are included. Examples of useful lipases includelipases from Humicola (synonym Thermomyces), e.g., from H. lanuginosa(T. lanuginosus), or from H. insolens, a Pseudomonas lipase, e.g., fromP. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P.fluorescens, Pseudomonas sp. strain SD 705, P. wisconsinensis, aBacillus lipase, e.g., from B. subtilis, B. stearothermophilus or B.pumilus.

The lipase may be a “first cycle lipase”, preferably a variant of thewild-type lipase from Thermomyces lanuginosus comprising T231R and N233Rmutations. The wild-type sequence is the 269 amino acids (amino acids23-291) of the Swissprot accession number Swiss-Prot 059952 (derivedfrom Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipaseswould include those sold under the tradenames Lipex®, Lipolex® andLipoclean® by Novozymes, Bagsvaerd, Denmark.

Preferably, the composition comprises a variant of Thermomyceslanuginosa (O59952) lipase having >90% identity with the wild type aminoacid and comprising substitution(s) at T231 and/or N233, preferablyT231R and/or N233R.

In another aspect, the composition comprises a variant of Thermomyceslanuginosa (O59952) lipase having >90% identity with the wild type aminoacid and comprising substitution(s):

(a) S58A+V60S+I83T+A150G+L227G+T231R+N233R+I255A+P256K;

(b) S58A+V60S+I86V+A150G+L227G+T231R+N233R+I255A+P256K;

(c) S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(d)S58A+V60S+I86V+T143S+A150G+G163K+S216P+L227G+T231R+N233R+I255A+P256K;

(e) E1*+S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(f) S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(g)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K+L259F;

(h)S58A+V60S+I86V+K98I+E99K+D102A+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(i) N33Q+S58A+V60S+I86V+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(j)E1*+S58A+V60S+I86V+K98I+E99K+T143S+A150G+L227G+T231R+N233R+I255A+P256K;

(k)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+S216P+L227G+T231R+N233R+I255A+P256K;

(l) D27N+S58A+V60S+I86V+G91N+N94R+D1UN+T143S+A150G+L227G+T231R+N233R+1255A+P256K;

(m)E1N+S58A+V60S+I86V+K98I+E99K+T143S+A150G+E210A+S216P+L227G+T231R+N233R+1255A+P256K;

(n) A150G+E210V+T231R+N233R+I255A+P256K; and

(o) I202L+E210G+T231R+N233R+I255A+P256K.

When lipase is present, it is preferred that the pH tuneableamido-gellant comprises no ester-bonds, since some di-amido gellantsthat comprise ester-bonds may be hydrolyzed by the lipase enzyme, unlessthe lipase enzyme is encapsulated.

Xyloglucanase: Suitable xyloglucanase enzymes have enzymatic activitytowards both xyloglucan and amorphous cellulose substrates, wherein theenzyme is a glycosyl hydrolase (GH) is selected from GH families 5, 12,44 or 74. Preferably, the glycosyl hydrolase is selected from GH family44. Suitable glycosyl hydrolases from GH family 44 are the XYG1006glycosyl hydrolase from Paenibacillus polyxyma (ATCC 832) and variantsthereof.

Pectate lyase: Suitable pectate lyases are either wild-types or variantsof Bacillus-derived pectate lyases (CAF05441, AAU25568) sold under thetradenames Pectawash®, Pectaway® and X-Pect® (from Novozymes A/S,Bagsvaerd, Denmark).

Mannanase: Suitable mannanases are sold under the tradenames Mannaway®(from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (GenencorInternational Inc., Palo Alto, Calif.).

Bleaching enzyme: Suitable bleach enzymes include oxidoreductases, forexample oxidases such as glucose, choline or carbohydrate oxidases,oxygenases, catalases, peroxidases, like halo-, chloro-, bromo-,lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases(phenoloxidases, polyphenoloxidases). Suitable commercial products aresold under the Guardzyme® and Denilite® ranges from Novozymes.Advantageously, additional, preferably organic, particularly preferablyaromatic compounds are incorporated with the bleaching enzyme; thesecompounds interact with the bleaching enzyme to enhance the activity ofthe oxidoreductase (enhancer) or to facilitate the electron flow(mediator) between the oxidizing enzyme and the stain typically overstrongly different redox potentials.

Other suitable bleaching enzymes include perhydrolases, which catalysethe formation of peracids from an ester substrate and peroxygen source.Suitable perhydrolases include variants of the Mycobacterium smegmatisperhydrolase, variants of so-called CE-7 perhydrolases, and variants ofwild-type subtilisin Carlsberg possessing perhydrolase activity.

Cutinase: Suitable cutinases are defined by E.C. Class 3.1.1.73,preferably displaying at least 90%, or 95%, or most preferably at least98% identity with a wild-type derived from one of Fusarium solani,Pseudomonas Mendocina or Humicola Insolens.

Identity: The relativity between two amino acid sequences is describedby the parameter “identity”. For purposes of the present invention, thealignment of two amino acid sequences is determined by using the Needleprogram from the EMBOSS package (http://emboss.org) version 2.8.0. TheNeedle program implements the global alignment algorithm described inNeedleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. Thesubstitution matrix used is BLOSUM62, gap opening penalty is 10, and gapextension penalty is 0.5.

Enzymes, particularly protease and lipase, may be encapsulated. Suitableencapsulated enzymes may be prepared by methods such as:

-   -   (i) interfacial condensation polymerization, including capsules        formed by the reaction of acid chlorides with compounds        containing at least two amine groups and polycondensation        reaction of formaldehyde with melamine. Examples of such methods        are disclosed in U.S. Pat. Nos. 4,906,396, 6,221,829, 6,359,031,        6,242,405 and WO 07/100501 A2.    -   (ii) sol-gel processes including capsules made by reaction of        aminoalkylsilane precursors and aminoalkyl-trialkoxysilane, and        one or more alkoxysilane precursors, examples of which are        disclosed in WO 05/028603 A1 and WO 05/028604 A1; and    -   (iii) polyectrolyte precipitation, including capsules formed by        reaction of chitosan and alginate or using biopolymer gels such        as gellan. Examples of such methods are disclosed in EP        1,502,645 A1.    -   (iv) Spray drying, including capsules derived from spray drying        mixtures comprising at least one cellulosic polymer selected        from the group consisting of hydroxypropyl methylcellulose        phthalate (HPMCP), cellulose acetate phthalate (CAP), and        mixtures thereof. Such polymers include polymers that are        commercially available under the trade names NF Hypromellose        Phthalate (HPMCP) (Shin-Etsu), cellulose ester NF or cellulose        cellacefate NF (CAP) from G.M. Chemie Pvt Ltd, Mumbai, 400705,        India and Eastman Chemical Company, Kingsport, USA. Examples of        such methods are disclosed in WO/2011/005943.

The encapsulated protease may comprise at least 0.5%, or at least 1%, orat least 2%, or at least 5%, or at least 10%, or even at least 20% byweight active protease enzyme.

Encapsulated proteases may comprise from about 5% to about 90% activeprotease by weight.

Encapsulated proteases may be incorporated into the compositions of thepresent invention, based on total cleaning composition weight, at alevel of from 0.001% to about 30%, or from about 0.005% to about 25%, orfrom about 0.05% to about 10% or even from about 0.01% to about 2%.

Without wishing to be bound by theory, it is believed that having a lowparticle size facilitates the liquid phase's ability to suspend theparticles, thereby keeping the liquid phase as homogenous as possible.When said encapsulated proteases are in the form of enzymemicrocapsules, said microcapsules typically have a particle size of fromabout 100 microns to about 0.05 microns, from about 80 microns to about0.05 microns, or even from about 50 microns to about 0.05 microns. Thus,in one aspect, such microcapsules are sized such that they are nottypically visible to a consumer when such microcapsules are incorporatedinto a cleaning composition.

Preferably, the encapsulated protease releases at least 80% of itsprotease load within 10 minutes, within 5 minutes, or even within 2minutes upon dilution in the wash. These release rates are preferablyachievable at ambient temperatures under a 100 fold dilution at 20° C.with stirring at 150 rpm. Protease activity can be determined by anystandard method such as use of protease analysis kits available fromSigma Aldrich, Milwaukee, Wis., USA or ASTM method D0348-89 (2003).Without wishing to be bound by theory, it is believed that a bettercleaning profile is obtained as the time that the enzymes have tointeract with the soil is increased.

Encapsulated proteases may be enzyme granulates/prills, having anaverage particle size of 200-1000 microns. Such enzyme granules/prillsmay be made in accordance with the teachings of U.S. Pat. Nos.4,106,991, 4,242,219, 4,689,297, 5,324,649 and 7,018,821 B2. In oneaspect, such enzyme granulates/prills may comprise a dye and/or pigment.In one aspect, such enzyme granulates/prills may comprise a coatingcomprising hydroxpropylmethylcellulose and/or polyvinylalcohol andderivatives thereof.

3. Enzyme Stabilizers

Suitable mass efficient reversible protease inhibitors for theinhibition of serine proteases would include derivates of boronic acid,especially derivatives of phenyl boronic acid and peptide aldehydes,including tripeptide aldehydes. Examples of such compounds are disclosedin WO 98/13458 A1, WO 07/113241 A1, and U.S. Pat. No. 5,972,873.

The stabilizer may be selected from the group consisting of thiophene-2boronic acid, thiophene-3 boronic acid, acetamidophenyl boronic acid,benzofuran-2 boronic acid, naphtalene-1 boronic acid, naphtalene-2boronic acid, 2-fomyl phenyl boronic acid (2-FPBA), 3-FBPA, 4-FPBA,1-thianthrene boronic acid, 4-dibenzofuran boronic acid,5-methylthiophene-2 boronic, acid, thionaphtrene boronic acid, furan-2boronic acid, furan-3 boronic acid, 4,4 biphenyldiboronic acid,6-hydroxy-2-naphtalene, 4-(methylthio)phenyl boronic acid, 4(trimethylsilyl)phenyl boronic acid, 3-bromothiophene boronic acid,4-methylthiophene boronic acid, 2-naphtyl boronic acid, 5-bromothipheneboronic acid, 5-chlorothiophene boronic acid, dimethylthiophene boronicacid, 2-bromophenyl boronic acid, 3-chlorophenyl boronic acid,3-methoxy-2-thiophene, p-methyl-phenylethyl boronic acid, 2-thianthreneboronic acid, di-benzothiophene boronic acid, 4-carboxyphenyl boronicacid, 9-anthryl boronic acid, 3,5 dichlorophenyl boronic, acid, diphenylboronic acidanhydride, o-chlorophenyl boronic acid, p-chlorophenylboronic acid m-bromophenyl boronic acid, p-bromophenyl boronic acid,p-fluorophenyl boronic acid, p-tolyl boronic acid, o-tolyl boronic acid,octyl boronic acid, 1,3,5 trimethylphenyl boronic acid,3-chloro-4-flourophenyl boronic acid, 3-aminophenyl boronic acid,3,5-bis-(trifluoromethyl)phenyl boronic acid, 2,4 dichlorophenyl boronicacid, 4-methoxyphenyl boronic acid and mixtures thereof. Furthersuitable boronic acid derivatives suitable as stabilizers are describedin U.S. Pat. Nos. 4,963,655, 5,159,060, WO 95/12655, WO 95/29223, WO92/19707, WO 94/04653, WO 94/04654, U.S. Pat. Nos. 5,442,100, 5,488,157and 5,472,628.

Suitable mass efficient reversible protease inhibitors may comprise4-formyl phenyl boronic acid.

The mass efficient reversible protease inhibitor may comprise areversible peptide protease inhibitor. Examples of suitable reversiblepeptide protease inhibitors and processes for making same may be foundin U.S. Pat. No. 6,165,966 and WO 98/13459 A1.

Suitable tripeptide enzyme inhibitors may have the following structure:

The mass efficient reversible protease inhibitor may comprise a proteaseinhibitor of the protein type such as RASI, BASI, WASI (bifunctionalalpha-amylase/subtilisin inhibitors of rice, barley and wheat) asdisclosed in WO09/095425 or SSI (streptomyces subtilisin inhibitor) andvariants thereof as disclosed in Protein Engineering Design & Selection,vol 17 no. 4, p. 333-339, 2004.

4. Polymer Deposition Aids

Preferably, the fluid detergent composition comprises from 0.1% to 7%,more preferably from 0.2% to 3%, of a polymer deposition aid. As usedherein, “polymer deposition aid” refers to any cationic polymer orcombination of cationic polymers that significantly enhance depositionof a care benefit agents onto substrates (such as fabric) during washing(such as laundering). Suitable polymer deposition aids can comprise acationic polysaccharide and/or a copolymer. “Fabric care benefit agent”as used herein refers to any material that can provide fabric carebenefits. Non-limiting examples of fabric care benefits include, but arenot limited to: fabric softening, color protection, color restoration,pill/fuzz reduction, anti-abrasion and anti-wrinkling Non-limitingexamples of fabric care benefit agents include: silicone derivatives,oily sugar derivatives, dispersible polyolefins, polymer latexes,cationic surfactants and combinations thereof.

5. Cleaning Polymers

The detergent compositions herein may optionally contain from 0.01 to10% by weight of one or more cleaning polymers that provide forbroad-range soil cleaning of surfaces and fabrics and/or suspension ofthe soils. Any suitable cleaning polymer may be of use. Useful cleaningpolymers are described in US 2009/0124528A1. Non-limiting examples ofuseful categories of cleaning polymers include: amphiphilic alkoxylatedgrease cleaning polymers; clay soil cleaning polymers; soil releasepolyers; and soil suspending polymers.

6. Bleaching Systems

One embodiment is a composition, wherein the composition is a fluidlaundry bleach additive comprising from 0.1% to 12% by weight of ableach or bleach system, preferably a peroxide bleach, and furthercomprises a neat pH of from 2 to 6. Another embodiment is a fluidlaundry detergent composition comprising: from 0.1% to 12% by weight ofthe bleach, and a composition pH of from 6.5 to 10.5. Suitable hydrogenperoxide sources are described in detail in Kirk Othmer's Encyclopediaof Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp.271-300 “Bleaching Agents (Survey)”, and include the various forms ofsodium perborate and sodium percarbonate, including various coated andmodified forms. For example, hydrogen peroxide itself; perborates, e.g.,sodium perborate (any hydrate but preferably the mono- ortetra-hydrate); sodium carbonate peroxyhydrate or equivalentpercarbonate salts; sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Compositions of the presentinvention may also comprise as the bleaching agent a chlorine-typebleaching material. Such agents are well known in the art, and includefor example sodium dichloroisocyanurate (“NaDCC”). However,chlorine-type bleaches are less preferred for compositions comprisingenzymes. They bleaching systems of use in the present invention may alsoinclude ingredients selected from the group consisting of: bleachactivators, hydrogen peroxide, hydrogen peroxide sources, organicperoxides, metal-containing bleach catalysts, transition metal complexesof macropolycyclic rigid ligands, other bleach catalysts, preformedperacids, photobleaches and mixtures thereof.

Bleach Activators: The peroxygen bleach component in the composition canbe formulated with an activator (peracid precursor), present at levelsof from 0.01 to 15%, preferably from 0.5 to 10%, more preferrably from1% to 8% by weight of the composition. Preferred activators are selectedfrom the group consisting of: tetraacetyl ethylene diamine (TAED),benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam,3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS),nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz),decanoyloxybenzenesulphonate (C₁₀-OBS), benzoylvalerolactam (BZVL),octanoyloxybenzenesulphonate (C₈-OBS), perhydrolyzable esters andmixtures thereof, alternatively benzoylcaprolactam andbenzoylvalerolactam, 4-[N-(nonaoyl)amino hexanoyloxyl]-benzene sulfonatesodium salt (NACA-OBS) (See U.S. Pat. No. 5,523,434),dodecanoyloxy-benzenesulphonate (LOBS or C₁₂-OBS),10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position), and decanoyloxybenzoic acid (DOBA) and mixturesthereof. Non-limiting examples of suitable bleach activators, includingquaternary substituted bleach activators, are described in U.S. Pat. No.6,855,680.

Hydrogen Peroxides sources: Suitable examples include inorganicperhydrate salts, including alkali metal salts such as sodium salts ofperborate (usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. When employed,inorganic perhydrate salts are typically present in amounts of from0.05% to 40%, preferably from 1% to 30% by weight of the composition.

Organic Peroxides: Diacyl Peroxides that do not cause visible spottingor filming are particularly preferred. One example is dibenzoylperoxide. Other suitable examples are illustrated in Kirk Othmer,Encyclopedia of Chemical Technology at 27-90, v. 17, John Wiley andSons, (1982).

Metal-containing Bleach Catalysts: Preferred bleach catalysts includemanganese and cobalt-containing bleach catalysts. Other suitablemetal-containing bleach catalysts include catalyst systems comprising atransition metal cation of defined bleach catalytic activity, such ascopper, iron, titanium, ruthenium tungsten, molybdenum, or manganesecations; an auxiliary metal cation having little or no bleach catalyticactivity, such as zinc or aluminum cations; and a sequestrate havingdefined stability constants for the catalytic and auxiliary metalcations, particularly ethylenediaminetetraacetic acid,ethylenediaminetetra (methylenephosphonic acid) and water-soluble saltsthereof. Suitable catalyst systems are disclosed in U.S. Pat. No.4,430,243.

Transition Metal Complexes of Macropolycyclic Rigid Ligands: The fluiddetergent compositions herein may also include bleach catalystscomprising a transition metal complex of a macropolycyclic rigid ligand.The amount used is preferably more than 1 ppb, more preferably 0.001 ppmor more, even more preferably from 0.05 ppm to 500 ppm (wherein “ppb”denotes parts per billion by weight and “ppm” denotes parts per millionby weight).

Other Bleach Catalysts: Other bleach catalysts such as organic bleachcatalysts and cationic bleach catalysts are suitable for the fluiddetergent compositions of the invention. Organic bleach catalysts areoften referred to as bleach boosters. The fluid detergent compositionsherein may comprise one or more organic bleach catalysts to improve lowtemperature bleaching. Preferred organic bleach catalysts arezwitterionic bleach catalysts, including aryliminium zwitterions.Suitable examples include 3-(3,4-dihydroisoquinolinium)propane sulfonateand 3,4-dihydro-2[2-(sulfooxy)decyl]isoquinolimium. Suitable aryliminiumzwitterions include:

wherein R¹ is a branched alkyl group containing from 9 to 24 carbons orlinear alkyl group containing from 11 to 24 carbons. Preferably, each R¹is a branched alkyl group containing from 9 to 18 carbons or linearalkyl group containing from 11 to 18 carbons, more preferably each R¹ isselected from the group consisting of 2-propylheptyl, 2-butyloctyl,2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl,n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl.Other suitable examples of organic bleach catalysts can be found in U.S.Pat. No. 5,576,282 and U.S. Pat. No. 5,817,614, EP 923,636 B1, WO2001/16263 Al, WO 2000/42156 A1, WO 2007/001262 A1.

Suitable examples of cationic bleach catalysts are described in U.S.Pat. Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515,5,550,256, WO 95/13351, WO 95/13352, and WO 95/13353.

Preformed peracids: The preferred preformed peracid is Phthalimidoperoxycaproic acid (PAP). Other suitable preformed peracids include, butare not limited to, compounds selected from the group consisting of:percarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, and mixturesthereof. In compositions such as bleach containing fluid laundrydetergents, the preformed peracid may be present at a level of from 0.1%to 25%, preferably from 0.5% to 20%, more preferably from 1% to 10%,most preferably from 2% to 4% by weight of the composition.Alternatively, higher levels of peracid may be present. For instance,compositions such as fluid laundry bleach additives may comprise from10% to 40%, preferably from 15% to 30%, more preferably from 15% to 25%by weight preformed peracid.

7. Optical Brighteners

These are also known as fluorescent whitenening agents for textiles.Preferred levels are from 0.001% to 1% by weight of the fluid detergentcomposition. Suitable brighteners are disclosed in EP 686691B andinclude hydrophobic as well as hydrophilic types. Brightener 49 ispreferred for use in the present invention.

8. Hueing Dyes

Hueing dyes or fabric shading dyes are useful adjuncts in fluiddetergent compositions.

Suitable dyes include blue and/or violet dyes having a hueing or shadingeffects. The fluid detergent compositions herein may comprise from0.00003% to 0.1%, preferably from 0.00008% to 0.05%, more preferablyfrom 0.0001% to 0.04% by weight of the fabric hueing dye.

9. Particulate Material

The fluid detergent composition may include particulate material such asclays, suds suppressors, encapsulated sensitive ingredients, e.g.,perfumes including perfume microcapsules, bleaches and enzymes inencapsulated form; or aesthetic adjuncts such as pearlescent agentsincluding mica, pigment particles, or the like. Suitable levels are from0.0001% to 5%, or from 0.1% to 1% by weight of the fluid detergentcomposition.

10. Perfume and Odour Control Agents

In preferred embodiments, the fluid detergent composition comprises aperfume. If present, perfume is typically incorporated at a level from0.001 to 10%, preferably from 0.01% to 5%, more preferably from 0.1% to3% by weight of the composition. The perfume may comprise a perfumemicrocapsule and/or a perfume nanocapsule. In other embodiments, thefluid detergent composition comprises odour control agents such asuncomplexed cyclodextrin as described in U.S. Pat. No. 5,942,217.

11. Hydrotropes

The fluid detergent composition optionally comprises a hydrotrope in aneffective amount, i.e. up to 15%, preferably 1% to 10%, more preferably3% o 6% by weight, so that the fluid detergent compositions arecompatible in water. Suitable hydrotropes for use herein includeanionic-type hydrotropes, particularly sodium, potassium, and ammoniumxylene sulfonate, sodium, potassium and ammonium toluene sulfonate,sodium potassium and ammonium cumene sulfonate, and mixtures thereof, asdisclosed in U.S. Pat. No. 3,915,903.

Unit Dose Detergent:

In some embodiments of the present invention, the fluid detergentcomposition is enclosed within a water soluble pouch material. Preferredpolymers, copolymers or derivatives thereof suitable for use in pouchmaterials are selected from the group: polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose,cellulose ethers, cellulose esters, cellulose amides, polyvinylacetates, polycarboxylic acids and salts, polyaminoacids or peptides,polyamides, polyacrylamide, copolymers of maleic/acrylic acids,polysaccharides including starch and gelatin, natural gums such asxanthum and carragum. More preferred polymers are selected frompolyacrylates and water-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof.

Process of Making:

The present invention also includes a process for making a fluiddetergent composition incorporating a pH tuneable amido gellant,comprising the steps of:

-   -   a) preparing a structurant premix comprising the pH tuneable        amido gellant, wherein the structurant premix is at a pH such        that the pH tuneable amido gellant is in its ionic,        non-viscosity building, form;    -   b) combining the structurant premix with a detergent feed, said        detergent feed comprising an anionic and/or nonionic surfactant;    -   c) adjusting the pH of the combined fluid detergent composition        as needed, such that the fluid detergent composition is at a pH        at which the pH tuneable amido gellant is in its nonionic,        viscosity building, form.

The fluid detergent compositions comprising a pH tuneable amido gellantis preferably processed such that the temperatures of the structurantpremix and/or the ingredient stream are maintained at less than 50° C.,preferably less than 30° C.; particularly if the fluid detergentcomposition further incorporates temperature-sensitive ingredients suchas enzymes or perfumes.

Test Methods:

-   1. Turbidity (NTU):

Turbidity (measured in NTU: Nephelometric Turbidity Units) according tothe present invention is measured using a Hach 2100P turbidity metercalibrated according to the procedure provided by the manufacture. Thesample vials are filled with 15 ml of representative sample and cappedand cleaned according to the operating instructions. If necessary, thesamples are degassed to remove any bubbles either by applying a vacuumor using an ultrasonic bath (see operating manual for procedure). Theturbidity is measured using the automatic range selection.

-   2. Minimum Gelling Concentration (MGC)

MGC is calculated by a tube inversion method based on R. G. Weiss, P.Terech; “Molecular Gels: Materials with self-assembled fibrillarstructures” 2006 springer, p 243. In order to determine the MGC, threescreenings are done:

-   -   a) First screening: prepare several vials increasing the pH        tuneable amido gellant concentration from 0.5% to 5.0 weight %        in 0.5% steps, at the target pH.    -   b) Determine in which interval the gel is formed (one inverted        sample still flowing and the next one is already a strong gel).        In case no gel is formed at 5%, higher concentrations are used.    -   c) Second screening: prepare several vials increasing the pH        tuneable amido gellant concentration in 0.1 weight % steps in        the interval determined in the first screening, at the target        pH.    -   d) Determine in which interval the gel is formed (one inverted        sample still flowing and the next one is already a strong gel)    -   e) Third screening: in order to have a very precise percentage        of the MGC, run a third screening in 0.025 weight % steps in the        interval determined in the second screening, at the target pH.    -   f) The Minimum Gelling Concentration (MGC) is the lowest        concentration which forms a gel in the third screening (does not        flow on inversion of the sample).

For each screening, samples are prepared and treated as follows: 8 mLvials (Borosilacate glass with Teflon cap, ref. B7857D, FisherScientific Bioblock) are filled with 2.0000±0.0005 g (KERN ALJ 120-4analytical balance with ±0.1 mg precision) of the fluid (comprising thefluid detergent composition and pH tuneable amido gellant) for which wewant to determine the MGC. The vial is sealed with the screw cap andleft for 10 minutes in an ultrasound bath (Elma Transsonic T 710 DH, 40kHz, 9.5 L, at 25° C. and operating at 100% power) in order to dispersethe solid in the liquid. Complete dissolution is then achieved byheating, using a heating gun (Bosch PHG-2), and gentle mechanicalstirring of the vials. It is crucial to observe a completely clearsolution. Handle vials with care. While they are manufactured to resisthigh temperatures, a high solvent pressure may cause the vials toexplode. Vials are cooled to 25° C., for 10 min in a thermostatic bath(Compatible Control Thermostats with controller CC2, D77656, Huber).Vials are inverted, left inverted for 1 minute, and then observed forwhich samples do not flow. After the third screening, the concentrationof the sample that does not flow after this time is the MGC. For thoseskilled in the art, it is obvious that during heating solvent vapoursmay be formed, and upon cooling down the samples, these vapours cancondense on top of the gel. When the vial is inverted, this condensedvapour will flow. This is discounted during the observation period. Ifno gels are obtained in the concentration interval, higherconcentrations must be evaluated.

-   3. pH Measurement of a Liquid Detergent Composition

pH measurement of a liquid detergent composition may be measured usingtest method EN 1262.

-   4. Rheology

An AR-G2 rheometer from TA Instruments is used for rheologicalmeasurements. Plate: 40 mm standard steel parallel plate, 300 μm gap.

-   1. Gel strength: The gel strength is measured using a stress sweep    test whereby the oscillation stress is increased from 0.001 Pa to 10    Pa, taking 10 points per decade at 20° C. and at a frequency of 1    Hz. We use G′ and G″ within the linear viscoelastic region and the    oscillation stress at the point where G′ and G″ cross over as a    measure for the gel strength, as shown in FIG. 1.-   2. Recovery of structure: first we apply a pre-shear of 30 s-1 at    20° C. for 60 s, after which we follow how the structure recovers    applying a time sweep test with an oscillation stress of 0.02 Pa and    a single frequency of 1 Hz at 20° C. for 10 minutes. As a measure of    the restructuring kinetics, we use G′ and G″ cross over, as shown in    the FIG. 2.

EXAMPLES Example 1 A Liquid Laundry Detergent Composition According tothe Present Invention is Prepared as Follows

-   Step 1: A structurant premix A1 is prepared by dissolving 0.20 grams    N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide    in 12.0 grams of 50% citric acid aqueous solution (prepared by    dissolving 6.0 grams of citric acid solid in 6.0 grams deionized    water) at 25° C.-   Step 2: A detergent feed B1 having the composition described in    Table 4 is prepared.

TABLE 4 Composition of detergent feed B1 Detergent Feed B1 IngredientGrams Linear Alkylbenzene sulfonic acid (LAS) 12.0 C12-14 alkyl ethoxy 3sulfate Mono Ethanol 9.3 Amine salt C12-14 alkyl 7-ethoxylate 8.01,2-propanediol 9.8 C12-18 Fatty Acid 10.0 Grease Cleaning AlkoxylatedPolyalkylenimine 0.9 Polymer¹ PEG PVAc Polymer² 0.9 Soil SuspendingAlkoxylated Polyalkylenimine 2.2 Polymer³ Hydroxyethane diphosphonicacid 1.6 FWA 0.23 Ethanol 1.5 Boric acid 0.5 MEA Up to pH 8 Water up to66 grams ¹600 g/mol molecular weight polyethylenimine core with 24ethoxylate groups per —NH and 16 propoxylate groups per —NH. ²PEG-PVAgraft copolymer is a polyvinyl acetate grafted polyethylene oxidecopolymer having a polyethylene oxide backbone and multiple polyvinylacetate side chains. The molecular weight of the polyethylene oxidebackbone is 6000 and the weight ratio of the polyethylene oxide topolyvinyl acetate is 40 to 60 and no more than 1 grafting point per 50ethylene oxide units. ³600 g/mol molecular weight polyethylenimine corewith 20 ethoxylate groups per —NH.

-   Step 3: 12.4 grams of structurant premix A1 is mixed with 66 grams    of detergent feed B1 at 600 rpm for 10 min, at 25° C., and the    resulting mixture is adjusted to pH 8 with MEA.

Step 4: The pH sensitive ingredients (1.5 grams protease, 0.7 gramsamylase, 0.1 grams mannanase, 0.1 grams xyloglucanase, 0.4 grams pectatelyase and 1.7 grams of perfume) and deionized water (to bring the finalweight up to 100 grams) are added under gentle stirring, at 500-600 rpmfor 10 min.

Example 2 Unit Dose Laundry Detergent

A laundry unit dose comprising the fluid detergent composition of thepresent invention is prepared as follows:

-   Step 1: A structurant premix A2 is prepared by fully dissolving 0.20    grams    N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide    in 1.0 grams of citric acid and 3 grams of deionized water at 25° C.-   Step 2: A detergent feed B2 having the composition described in    Table 5 is prepared.

TABLE 5 Composition of detergent feed B2 Detergent Feed B2 % of base @Ingredient 100% active 1,2-Propanediol 15 MEA 10 Glycerol 5Hydroxyethane diphosphonic acid 1 Potassium sulfite 0.2 C12-45 alkyl7-ethoxylate 20 Linear Alkylbenzene sulfonic acid 24.5 FWA 0.2 C12-18Fatty Acid 16 Ethoxysulfated Hexamethylene Diamine 2.9 Dimethyl QuatSoil Suspending Alkoxylated Polyalkylenimine 1 Polymer³ MgCl₂ 0.2 Waterand minors Up to 100%

-   Step 3: 4.2 grams of structurant premix A2 are mixed with 34.5 grams    of detergent feed B2 at 600 rpm for 10 min, at 25° C., for 5    minutes. The resulting mixture is adjusted to pH 8 with MEA and pH    sensitive ingredients listed in Table 6 are added at 600 rpm, 25°    C., and mixed for 2 minutes:

TABLE 6 pH sensitive ingredients. % of base @ Ingredient 100% activeProtease enzyme 1.4 Mannanase enzyme 0.1 Amylase enzyme 0.2The fluid detergent composition is then packed into a polyvinyl alcoholpouch.

Examples 3A to 3E Fluid Detergent Fabric Care Compositions ComprisingAmido-Gellants of the Present Invention

-   Step 1: A structurant premix A3 is prepared by dissolving 5 grams    N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide    in 95 grams of 25% sulfuric acid aqueous solution (Sigma-Aldrich) at    25° C.-   Step 2: A detergent feed B3A to B3E having the composition described    in Table 7 is prepared.

TABLE 7 Composition of detergent feed B3A to B3E B3A B3B B3C B3D B3EIngredient Wt % Wt % Wt % Wt % Wt % C12-15 alkyl polyethoxylate 6.7 6.57.8 6.4 5.7 (3.0) sulfate C11.8 linear alkylbenzene 19.4  18.9  19.0 14.6  16.4  sulfonc acid C14-15 alkyl 7-ethoxylate 11.8  11.5  3.9 4.816.4  C12-14 alkyl 7-ethoxylate — 0.9 1.0 1.1 0.9 1,2 Propane diol 7.05.2 8.2 9.1 6.9 Ethanol 1.8 1.7 2.0 2.3 1.7 Di Ethylene Glycol — 3.4 — —— Na Cumene Sulfonate 5.3 5.2 6.1 6.8 5.2 C12-18 Fatty Acid 4.6 4.5 6.75.9 4.5 Citric acid 4.6 4.5 7.6 9.8 4.5 Fluorescent Whitening Agent 0.18 —  0.20  0.23  0.17 Diethylene Triamine Penta —  0.860 — — —Acetic acid Diethylene Triamine Penta  0.53  0.17  0.61  0.68  0.52Methylene Phosphonic acid Soil Suspending Alkoxylated 1.4 0.9 — — 1.4Polyalkylenimine Polymer¹ Zwitterionic ethoxylated 1.8 1.7 1.8 2.3 1.7quaternized sulfated hexamethylene diamine² Grease Cleaning Alkoxylated0.7 0.7 — 0.5 — Polyalkylenimine Polymer³ PEG-PVAc Polymer⁴ — 0.9 — — —Monoethanolamine Borate 3.5 1.7 4.1 4.6 3.4 4-Formyl Phenyl Boronic Acid—  0.05 — — — Sodium formate 0.7 0.7 0.8 0.9 0.7 Calcium chloride  0.09 0.09  0.10  0.11  0.09 Acticide MBS 2550  0.010  0.010  0.010  0.010 0.010 Water up to up to up to up to up to 100% 100% 100% 100% 100% ¹600g/mol molecular weight polyethylenimine core with 20 ethoxylate groupsper —NH. Available from BASF (Ludwigshafen, Germany) ²Described in WO01/05874 and available from BASF (Ludwigshafen, Germany) ³600 g/molmolecular weight polyethylenimine core with 24 ethoxylate groups per —NHand 16 propoxylate groups per —NH. Available from BASF (Ludwigshafen,Germany). ⁴PEG-PVA graft copolymer is a polyvinyl acetate graftedpolyethylene oxide copolymer having a polyethylene oxide backbone andmultiple polyvinyl acetate side chains. The molecular weight of thepolyethylene oxide backbone is about 6000 and the weight ratio of thepolyethylene oxide to polyvinyl acetate is about 40 to 60 and no morethan 1 grafting point per 50 ethylene oxide units. Available from BASF(Ludwigshafen, Germany).

-   Step 3: Structurant premix A3 (amounts listed in Table 8) is mixed    with 70 grams of detergent feeds B3A to B3E at 400 rpm for 10 min,    at 35° C.

TABLE 8 addition of premix A3 3A 3B 3C 3D 3E Ingredient grams gramsgrams grams grams Premix A3 5 3 4 6 3.6The resulting mixture is adjusted to pH 8 with sodium hydroxide 20% andpH sensitive ingredients listed in Table 9 are added at 600 rpm, 25° C.,and mixed for 5 minutes.

TABLE 9 pH sensitive ingredients. 3A 3B 3C 3D 3E Ingredient Wt % Wt % Wt% Wt % Wt % Protease (40.6 mg/g/)¹ 0.5  0.5  0.5  0.5  0.5  Natalase200L (29.26 mg/g)² 0.1  0.1  0.1  0.1  0.1  Termamyl Ultra (25.1 mg/g)²0.05 0.05 0.05 0.05 0.05 Mannaway 25L (25 mg/g)² 0.05 0.05 0.05 0.050.05 Lipase (16.91 mg/g)² 0.5  — 0.25 — 0.5  Lipolex ®² — 0.2  — — —Lipex ®² — — — 0.25 — Whitezyme (20 mg/g)² 0.05 0.05 0.05 0.05 0.05Perfume Microcapsules³ — — — 0.2  — Mica — — — — 0.05 Silicone sudssuppressor — 0.1  — — — Water, perfumes, dyes, to to to to toneutralizers, and other 100% 100% 100% 100% 100% optional components (pHto 8.0-8.2) ¹Available from Genencor International, South San Francisco,CA. ²Available from Novozymes, Denmark. ³Perfume microcapsules can beprepared as follows: 25 grams of butyl acrylate-acrylic acid copolymeremulsifier (Colloid C351, 25% solids, pka 4.5-4.7, Kemira Chemicals,Inc. Kennesaw, Georgia U.S.A.) is dissolved and mixed in 200 gramsdeionized water. The pH of the solution is adjusted to pH of 4.0 withsodium hydroxide solution. 8 grams of partially methylated methylolmelamine resin (Cymel 385, 80% solids, Cytec Industries West Paterson,New Jersey, U.S.A.) is added to the emulsifier solution. 200 grams ofperfume oil is added to the previous mixture under mechanical agitationand the temperature is raised to 50° C. After mixing at higher speeduntil a stable emulsion is obtained, the second solution and 4 grams ofsodium sulfate salt are added to the emulsion. This second solutioncontains 10 grams of butyl acrylate-acrylic acid copolymer emulsifier(Colloid C351, 25% solids, pka 4.5-4.7, Kemira), 120 grams of distilledwater, sodium hydroxide solution to adjust pH to 4.8, 25 grams ofpartially methylated methylol melamine resin (Cymel 385, 80% solids,Cytec). This mixture is heated to 70° C. and maintained overnight withcontinuous stirring to complete the encapsulation process. 23 grams ofacetoacetamide (Sigma-Aldrich, Saint Louis, Missouri, U.S.A.) is addedto the suspension.

Examples 4A to 4S Hand-Dish Washing Fluid Detergent CompositionsComprising Amido-Gellants

Hand-dish washing liquid detergent compositions may be prepared bymixing together the ingredients listed in the proportions shown:

TABLE 10 Hand-dish washing fluid detergent compositions comprisingamido-gellants Ex Ex Ex Ex Ex Ex 4A 4B 4C 4D 4E 4F Alkyl Ethoxy SulfateAE0.6S 22.0 19.0 27.0 20.0 22.0 22.0 Linear C12-C14 Amine oxide 6.0 4.5— — 6.0 5.0 C9-C11 alkyl EO8 ethoxylate 7.0 — — — — — L-Glutamicacid-N,N- 1.0 — — 0.1 — — di(acetic acid) tetrasodium salt SodiumCitrate — 1.0 — 0.5 0.8 — Solvent: ethanol, 2.5 4.0 3.0 2.0 3.0 2.5isopropylalcohol, . . . Polypropylene glycol 1.0 0.5 1.0 — 2.0 1.0Mw2000 Sodium Chloride 0.5 1.0 1.0 0.5 0.5 0.5N,N′-(2S,2′S)-1,1′-(dodecane- 0.05 0.20 0.10 0.15 0.25 0.201,12-diylbis(azanediyl))bis(3- methyl-1-oxobutane-2,1-diyl)diisonicotinamide Minors and Balance with water up to 100%

TABLE 11 Hand-dish washing fluid detergent compositions comprisingamido-gellants Ex 4G Ex 4H Ex 4I Ex 4J Alkyl Ethoxy Sulfate AE1.0S 13  16   17   20   C12-C14 Amine oxide 4.5 5.5 4.0 4.5 C9-C11 alkyl EO8ethoxylate 4   4   — — L-Glutamic acid-N,N-di(acetic acid) 0.7 — — —tetrasodium salt Sodium Citrate — — 0.2 — Solvent: ethanol,isopropylalcohol, . . . 2.0 2.0 2.0 1.5 Polypropylene glycol Mw2000 0.50.3 0.5 0.8 Sodium Chloride 0.5 0.8 0.4 0.5N,N′-(2S,2′S)-1,1′-(dodecane-1,12-  0.30  0.20  0.50  0.25diylbis(azanediyl))bis(3-methyl-1- oxobutane-2,1-diyl)diisonicotinamideMinors and Balance with water up to 100%

TABLE 12 Hand-dish washing fluid detergent compositions comprisingamido-gellants Ex Ex Ex Ex Ex 4K 4L 4M 4N 4O Linear AlkylbenzeneSulfonate 21.0  21.0  12.0 13.0  — Alkyl Ethoxy Sulfate AE1.0S — — 14.05.0 17.0  C12-14 alpha olefin sulfonate — — — — 6.0 Coco amido propylAmine Oxide — — — 1.0 5.0 alkylpolyglucoside — 2.0 — — — C9-C11 alkylEO8 ethoxylate 5.0 4.0  8.0 4.0 3.0 L-Glutamic acid-N,N-di(acetic 0.5 —— — — acid) tetrasodium salt N,N′-(2S,2′S)-1,1′-(dodecane-  0.15  0.15 0.10  0.20  0.10 1,12-diylbis(azanediyl))bis(3- methyl-1-oxobutane-2,1-diyl)diisonicotinamide Minors and Balance with water up to 100%

TABLE 13 Hand-dish washing fluid detergent compositions comprisingamido-gellants Ex 4P Ex 4Q Ex 4R Ex 4S Alkyl Ethoxy Sulfate AE2.0S 17.0 12.0  24.0  29.0  C12-14 alpha olefin sulfonate — — 1.0 — ParaffinSulfonate (C15) 9.0 1.0 1.0 — Coco amido propyl amine oxide — 6.0 — 1.0C12-C14 Akylpolyglucoside — 3.0 2.0 — C9-C11 alkyl EO8 ethoxylate 8.02.0 — — L-Glutamic acid-N,N-di(acetic 0.5 — 0.5 — acid) tetrasodium saltPolypropylene glycol MW2000 1.0 1.0 — 0.5 N,N′-(2S,2′S)-1,1′-(dodecane- 0.10  0.25  0.10  0.15 1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)di- isonicotinamide Minors and Balance withwater up to 100%N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamidehas been added as Premix A3 prepared in example 3. Afterwards, pH wasadjusted with 20% sodium hydroxide aqueous solution to pH 9 (forexamples 4A to 4J) and pH 8 (examples 4K to 4S).

Examples 5A, 5B and 5C Compacted Laundry Fluid Detergent Compositions(25 mL Dosage) Comprising Amido-Gellants

Step 1: A structurant premix A5 is prepared by dissolving 10 gramsN,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyediisonicotinamidein 90 grams 20% C₁₁₋₈ HLAS in 1,2-propanediol solution (prepared byadding 20 grams C₁₁₋₈ HLAS to 80 grams 1,2-propanediol at 50° C.) at 45°C.

Step 2: Detergent feeds BSA and B5B having the composition described inTable 14 are prepared.

TABLE 14 Composition of detergent feeds B5A, B5B, B5C 5A 5B 5CIngredients Weight % Monoethanolamine: 40.5  43.3  41.5  C₁₂₋₁₅EO•3•SO₃H Monoethanolamine: 6.5 7.4 7.0 C₁₆₋₁₇ highly soluble alkylsulfate C₁₂₋₁₄ dimethylamine- 1.9 2.1 2.0 N-oxide Ethoxylated 4.3 4.94.3 Polyethyleneimine¹ Citric acid — 2.5 1.0 Amphiphilic 4.3 3.1 4.3alkoxylated grease cleaning polymer² C₁₂₋₁₈ Fatty acid 3.3 — 3.3 Sudssuppression 0.1 0.1 0.1 polymer C₁₁₋₈ HLAS 14.7  12.4  13.0  HydroxyEthylidene — 1.2 — 1,1 Di Phosphonic acid Tiron 2.2 — 2.2 Brightener 0.10.2 0.1 Water 5.1 6.2 4.8 Minors (antioxidant, 1.6 1.9 2.0 sulfite,aesthetics, . . .) Buffers To pH 8.0 (monoethanolamine) Solvents (1,2 To100 parts propanediol, ethanol) ¹Polyethyleneimine (MW = 600 grams/mol)with 20 ethoxylate groups per —NH (BASF, Germany) ²PG617 or PG640 (BASF,Germany)

-   Step 3: Structurant premix AS (amounts listed in Table 15) are mixed    with detergent feeds BSA and B5B at 500 rpm for 10 min, at 45° C.,    for 5 minutes, then, product is cooled to 35° C. and pH is adjusted    to pH 8 with monoethanolamine Then, product is cooled to 25° C. and    perfume and/or perfume microcapsules are added according to table    15.

TABLE 15 addition of premix A5 and formula finishing 5A 5B 5CIngredients Weight % Detergent feed 75   75   75   Premix A5 2.5 3.0 6.0Monoethanolamine To pH 8.0 Perfume 1.5 1.7 1.3 Perfume 2.3 — 1.5microcapsules¹ Solvents (1,2 To 100 parts propanediol) ¹as described inexample 3

Examples 6A and 6B Laundry Fluid Detergent Composition ComprisingAmido-Gellants

Detergent feeds 6A and 6B, having the compositions described in Table16, are prepared. Then A3 premix is added and pH is adjusted to 8 withsodium hydroxide 20%.

TABLE 16 laundry fluid detergent composition comprising amido-gellants6A 6B Ingredient Wt % Wt % C12-14 alkyl polyethoxylate (3.0) sulfate 3.83.5 C₁₁₋₈ HLAS 3.7 4.0 C12-14 alkyl 7-ethoxylate 1.4 1.4 1,2 Propanediol 0.18 0.25 Glycerine 2.00 2.00 Diethylene triamine penta acetate0.48 0.48 Phenoxyethanol 0.1 0.1 Citric acid 1.70 2.5 FluorescentWhitening Agent 0.057 — Dodecyldimethylamine N-oxide 0.4 0.4Zwitterionic ethoxylated quaternized sulfated 0.25 0.25 hexamethylenediamine¹ Perfume 0.43 0.30 PEG-PVAc Polymer² 0.5 0.5 Silicone sudssupressor 0.0025 0.0025 Boric Acid 1.20 1.20 Calcium chloride 0.06 0.06Acticide MBS 2550 0.01 0.01 Premix A3 5.0 10.0 Sodium hydroxide 20% TopH 8 To pH 8 Water up to 100% up to 100% ¹Described in WO 01/05874 andavailable from BASF (Ludwigshafen, Germany) ²PEG-PVA graft copolymer isa polyvinyl acetate grafted polyethylene oxide copolymer having apolyethylene oxide backbone and multiple polyvinyl acetate side chains.The molecular weight of the polyethylene oxide backbone is 6000 and theweight ratio of the polyethylene oxide to polyvinyl acetate is 40 to 60and no more than 1 grafting point per 50 ethylene oxide units.

Example 7 Hand-Dish Washing Fluid Detergent Compositions ComprisingAmido-Gellant

Hand-dish washing liquid detergent compositions may be prepared bymixing together the ingredients listed in the proportions shown:

TABLE 17 Hand-dish washing fluid detergent compositions comprisingamido-gellant 7 Alkyl Ethoxy Sulfate AE2.0S 18.0 Coco amido propylBetaine 5.0 Polypropylene glycol MW2000 0.5N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(3- 0.25methyl-1-oxobutane-2,1-diyl)bis(4-hydroxybenzamide) Minors, citric acidand Balance with water up to 100% and pH 5.5.

Example 8 A Liquid Laundry Detergent Composition According to thePresent Invention is Prepared as Follows

-   Step 1: A structurant premix A1 is prepared by dissolving 0.20 grams    N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyediisonicotinamide    in 12.0 grams of 50% citric acid aqueous solution (prepared by    dissolving 6.0 grams of citric acid solid in 6.0 grams deionized    water) at 25° C.-   Step 2: A detergent feed B1 having the composition described in    Table 18 is prepared.

TABLE 18 Composition of detergent feed B1 Detergent Feed B1 IngredientGrams Linear Alkylbenzene sulfonic acid (LAS) 12.0 C12-14 alkyl ethoxy 3sulfate Mono Ethanol 9.3 Amine salt C12-14 alkyl 7-ethoxylate 8.01,2-propanediol 9.8 C12-18 Fatty Acid 10.0 Grease Cleaning AlkoxylatedPolyalkylenimine 0.9 Polymer¹ PEG PVAc Polymer² 0.9 Soil SuspendingAlkoxylated Polyalkylenimine 2.2 Polymer³ Hydroxyethane diphosphonicacid 1.6 FWA 0.23 Ethanol 1.5 Boric acid 0.5 MEA Up to pH 8 Water up to66 grams ¹600 g/mol molecular weight polyethylenimine core with 24ethoxylate groups per —NH and 16 propoxylate groups per —NH. ²PEG-PVAgraft copolymer is a polyvinyl acetate grafted polyethylene oxidecopolymer having a polyethylene oxide backbone and multiple polyvinylacetate side chains. The molecular weight of the polyethylene oxidebackbone is 6000 and the weight ratio of the polyethylene oxide topolyvinyl acetate is 40 to 60 and no more than 1 grafting point per 50ethylene oxide units. ³600 g/mol molecular weight polyethylenimine corewith 20 ethoxylate groups per —NH.

Step 3: 12.4 grams of structurant premix A1 is mixed with 66 grams ofdetergent feed B1 at 600 rpm for 10 min, at 25° C., and the resultingmixture is adjusted to pH 8 with MEA.

Step 4: The pH sensitive ingredients (1.5 grams protease, 0.7 gramsamylase, 0.1 grams mannanase, 0.1 grams xyloglucanase, 0.4 grams pectatelyase and 1.7 grams of perfume) and deionized water (to bring the finalweight up to 100 grams) are added under gentle stirring, at 500-600 rpmfor 10 min

Rheology Data

TABLE 19 Gel strength Oscillation Recovery Example n. G′ (Pa) G″ (Pa)stress (Pa) Time (s) 1 90 27 6.3 <6 5A 70 40 6.3 52 5C 8140 1540 >10 <66A 60 25 1.3 <6 6B 3030 730 8 <6 8 45 5 >10 <6

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A fluid detergent composition comprising: a) from 1% to 70% by weightof a surfactant selected from the group: anionic, nonionic surfactantsand mixtures thereof; and b) from 0.01 wt % to 10 wt % of a pH tuneableamido-gellant as an external structuring system having a formula

wherein: at least one of L₁, R₁ or R₂ comprises a pH-sensitive group; L₁is a backbone moiety having molecular weight from 14 to 500 g/mol; andR₁ is R₃ or

R₂ is R₄ or

wherein each AA is independently selected from the group consisting of:

and R₃ and R₄ independently have the formula: (L′)_(o)-(L″)_(q)-R,wherein: (o+q) is from 1 to 10; L′ and L″ are independently selectedfrom the group consisting of:

and R, R′ and R″ are independently selected either frompH-sensitive-groups consisting of:

wherein n and m are integers from 1 to 20; or from non-pH-sensitivegroups consisting of:

such that at least one of R, R′ and R″ comprises a pH-sensitive group;wherein the pH tuneable amido-gellant has a pKa of from 1 to
 30. 2. Afluid detergent composition according to claim 1, wherein the pHtuneable amido-gellant has a pKa of from 1.5 to
 14. 3. The fluiddetergent composition according to claim 1, wherein the pH tuneableamido-gellant has a molecular weight from 150 to 1500 g/mol.
 4. Thefluid detergent composition according to claim 1, wherein the pHtuneable amido-gellant has a minimum gelling concentration (MGC) of from0.1 to 100 mg/mL, at the pH of the composition.
 5. The fluid detergentcomposition according to claim 1, wherein the pH tuneable amido gellantis selected from the group consisting of:N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;(6S,13S′)-6,13-diisopropyl-4,7,12,15-tetraoxo-5,8,11,14-tetraazaoctadecane-1,18-dioicacid;(6S,14S″)-6,14-diisopropyl-4,7,13,16-tetraoxo-5,8,12,15-tetraazanonadecane-1,19-dioicacid;(6S,15S′)-6,15-diisopropyl-4,7,14,17-tetraoxo-5,8,13,16-tetraazaeicosane-1,20-dioicacid;(6S,16S′)-6,16-diisopropyl-4,7,15,18-tetraoxo-5,8,14,17-tetraazaheneicosane-1,21-dioicacid;(6S,17S′)-6,17-diisopropyl-4,7,16,19-tetraoxo-5,8,15,18-tetraazadocosane-1,22-dioicacid;(6S,18S′)-6,18-diisopropyl-4,7,17,20-tetraoxo-5,8,16,19-tetraazatricosane-1,23-dioicacid;(6S,19S′)-6,19-diisopropyl-4,7,18,21-tetraoxo-5,8,17,20-tetraazatetracosane-1,24-dioicacid;(6S,20S′)-6,20-diisopropyl-4,7,19,22-tetraoxo-5,8,18,21-tetraazapentacosane-1,25-dioicacid;(6S,21S′)-6,21-diisopropyl-4,7,20,23-tetraoxo-5,8,19,22-tetraazahexacosane-1,26-dioicacid;(6S,22S′)-6,22-diisopropy1-4,7,21,24-tetraoxo-5,8,20,23-tetraazapentacosane-1,27-dioicacid;(6S,23S′)-6,23-diisopropy1-4,7,22,25-tetraoxo-5,8,21,24-tetraazaoctacosane-1,28-dioicacid;N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamideN,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(nonane-1,9-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)bis(4-(1H-imidazol-5-yl)benzamide);N,N′-(2S,2′S)-1,1′-(nonane-1,9-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tridecane-1,13-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tetradecane-1,14-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexadecane-1,16-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octadecane-1,18-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(nonane-1,9-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tridecane-1,13-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tetradecane-1,14-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexadecane-1,16-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octadecane-1,18-diylbis(azanediyl))bis(1-oxopropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(ethane-1,2-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(butane-1,4-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(pentane-1,5-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexane-1,6-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamideN,N′-(2S,2′S)-1,1′-(heptane-1,7-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octane-1,8-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(nonane-1,9-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(decane-1,10-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(undecane-1,11-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tridecane-1,13-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(tetradecane-1,14-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(hexadecane-1,16-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;N,N′-(2S,2′S)-1,1′-(octadecane-1,18-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)diisonicotinamide;and mixtures thereof.
 6. The fluid detergent composition according toclaim 1, wherein the composition additionally comprises from 0.0001% to8% by weight of a detersive enzyme, and has a neat pH from 6.5 to 10.5.7. The fluid detergent composition according to claim 6, wherein thedetersive enzyme is selected from the group consisting of: proteases,amylases, cellulases, lipases, xylogucanases, pectate lyases,mannanases, bleaching enzymes, cutinases, and mixtures thereof.
 8. Thefluid detergent composition according to claim 1, wherein thecomposition is a fluid laundry detergent composition additionallycomprising from 0.1% to 12% by weight of the bleach or bleach system,and exhibits a neat pH of from 6.5 to 10.5.
 9. The fluid detergentcomposition according to claim 1, wherein the composition is a fluidlaundry bleach additive additionally comprising from 0.1% to 12% byweight of a bleach or bleach system, and exhibits a neat pH of from 2 to6.
 10. The fluid detergent composition according to claim 1, wherein thesurfactant is an anionic surfactant selected from the group consistingof: C11-C18 alkyl benzene sulfonates, C10-C20 branched-chain and randomalkyl sulfates, C10-C18 alkyl ethoxy sulfates, mid-chain branched alkylsulfates, mid-chain branched alkyl alkoxy sulfates, C10-C18 alkyl alkoxycarboxylates comprising 1-5 ethoxy units, modified alkylbenzenesulfonate, C12-C20 methyl ester sulfonate, C10-C18 alpha-olefinsulfonate, C6-C20 sulfosuccinates, and mixtures thereof.
 11. The fluiddetergent composition according to claim 1, wherein the compositionadditionally comprises an adjunct ingredient selected from the groupconsisting of: cationic surfactants, amphoteric and/or zwitterionicsurfactants, non-aminofunctional organic solvents, enzymes, enzymestabilizers, amphiphilic alkoxylated grease cleaning polymers, clay soilcleaning polymers, soil release polymers, soil suspending polymers,bleaching systems, optical brighteners, hueing dyes, particulatematerial, perfume and other odour control agents, hydrotropes, sudssuppressors, fabric care benefit agents, pH adjusting agents, dyetransfer inhibiting agents, preservatives, non-fabric substantive dyesand mixtures thereof.
 12. The fluid detergent composition according toclaim 1, wherein said fluid detergent composition is enclosed within awater soluble pouch material.
 13. A process for making a fluid detergentcomposition according to claim 1, comprising the steps of: a) preparinga structurant premix comprising the pH tuneable amido gellant, whereinthe structurant premix is at a pH such that the pH tuneable amidogellant is in its ionic, non-viscosity building, form; b) combining thestructurant premix with a detergent feed to form the detergentcomposition, said detergent feed comprising an anionic and/or nonionicsurfactant; c) adjusting the pH of the fluid detergent composition asneeded, such that the fluid detergent composition is at a pH at whichthe pH tuneable amido gellant is in its nonionic, viscosity building,form.
 14. A process, according to claim 13, for making a fluid detergentcomposition wherein the temperatures of the structurant premix and/orthe detergent feed are maintained at less than 50° C.